JPS62112716A - Dephosphorization method for molten metal containing chromium - Google Patents
Dephosphorization method for molten metal containing chromiumInfo
- Publication number
- JPS62112716A JPS62112716A JP60253463A JP25346385A JPS62112716A JP S62112716 A JPS62112716 A JP S62112716A JP 60253463 A JP60253463 A JP 60253463A JP 25346385 A JP25346385 A JP 25346385A JP S62112716 A JPS62112716 A JP S62112716A
- Authority
- JP
- Japan
- Prior art keywords
- dephosphorization
- molten metal
- carbonate
- flux
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/005—Manufacture of stainless steel
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/064—Dephosphorising; Desulfurising
- C21C7/0645—Agents used for dephosphorising or desulfurising
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/076—Use of slags or fluxes as treating agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Treatment Of Steel In Its Molten State (AREA)
Abstract
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、クロムを含む溶湯の脱燐方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for dephosphorizing molten metal containing chromium.
［従来技術］
鋼材中のＰは機械的性質や応力腐食割れに悪影響を及ぼ
すことが知られており、これを防止するためには低Ｐ化
を行なう必要がある０通常、溶鉄の場合はＣａＯフラッ
クスを使用して酸化脱燐を行なうが、Ｃｒなどの、酸化
されやすい元素を含む場合には、それらが優先的に酸化
されるため脱燐反応は進行しない、そこで、かかる場合
法のような脱燐方法が報告されて１．する。[Prior art] P in steel is known to have an adverse effect on mechanical properties and stress corrosion cracking, and in order to prevent this, it is necessary to reduce the P content.Normally, in the case of molten iron, CaO Oxidative dephosphorization is carried out using flux, but if it contains elements that are easily oxidized, such as Cr, these will be preferentially oxidized and the dephosphorization reaction will not proceed. A dephosphorization method has been reported.1. do.
（１）還元脱燐
５ｃａ−ＣａＦ２ 、ＣａＣ２−ＣａＦ２：ｙラックス
による脱燐（特許！３２７１３５．特詐１０１７３５１
） 。(1) Reductive dephosphorization 5ca-CaF2, CaC2-CaF2: Dephosphorization by y-lux (Patent! 327135. Special fraud 1017351
).
・Ｃａ、ＣａＣ２フラックスによる脱燐（特公昭５９−
５２９２６）。・Dephosphorization by Ca, CaC2 flux (Special Publication 1984-
52926).
これらは、３Ｃａ＋２Ｆ−＋Ｃａ３ Ｐ２ で表わされ
る反応を利用する方法である。These are methods that utilize the reaction represented by 3Ca+2F-+Ca3 P2.
（２）酸化脱燐
５Ｂａｏ−ＢａＣ１ｚ −Ｃｒｚ ０３系フランクブス
による脱燐（特開昭５８−３１０１０、特開昭５９−４
７３１６等）。(2) Oxidative dephosphorization 5Bao-BaC1z -Crz Dephosphorization by 03 series Frankbus (JP-A-58-31010, JP-A-59-4
7316 etc.).
これらはＰ酸化物であるＰ７０ｓ を。These are P70s which is P oxide.
ＣａＯより強塩ノ、（性の物質でスラグ中に固定する方
法である。This is a method of fixing CaO in the slag with a substance that is stronger than CaO.
［発明が解決しようとする問題点］ しかし、従来の上記技術には次のような問題点がある。[Problem to be solved by the invention] However, the above conventional technology has the following problems.
従来技術（１）について
脱燐処理後のスラグにはＣａ３Ｐ２が存在することにな
り、これが、大気中のＨ２０と、Ｃａ： Ｐ７ ＋３Ｈ
２０−＋ ３ＣａＯ＋２ＰＨ３テ示される式に従って反
応し、その結果にんにく匂の強い有害なフォスフイン（
ＰＨ３）を発生する。これを防止するためには脱燐処理
後のスラグの処理が必要である。Regarding conventional technology (1), Ca3P2 is present in the slag after dephosphorization treatment, and this is combined with H20 in the atmosphere and Ca: P7 +3H
20-+ 3CaO+2PH3 reacts according to the formula shown, resulting in the production of harmful phosphine (with a strong garlic odor).
PH3) is generated. To prevent this, it is necessary to treat the slag after dephosphorization.
従来技術（２）について
この方法はＢａＯ系フラフクスによる酸化脱燐法であり
、スラグの後処理が不要である。Regarding prior art (2), this method is an oxidative dephosphorization method using BaO-based fluff, and no post-treatment of the slag is required.
第１図に破線で示すように、ＢａＯまたはＢａＣ０，＋
系フラックスによる脱燐法ではスラグ−メタル間のＰ分
配比はスラブ塩基度（（ＢａＯ）／（Ｓｉ０２））が小
さくなると急激に低下する。スラグ中の５ｉ０２ は、
溶７易中のＳｌが脱燐処理中に酸化されて生成したもの
であり、また、脱Ｐ処理前の残留スラグおよび１′ｆＦ
１′大物から不１ｒ避的に混入してくるものである。従
って、脱燐率を高くするにはフラックスを多量に添加す
ることにより塩基度を高くする必要がある。As shown by the broken line in Figure 1, BaO or BaC0,+
In the dephosphorization method using a system flux, the P distribution ratio between slag and metal rapidly decreases as the slab basicity ((BaO)/(Si02)) decreases. 5i02 in the slag is
It is generated by the oxidation of Sl in the solution during dephosphorization, and it is also produced by the residual slag and 1'fF before dephosphorization.
1' This is something that inevitably gets mixed in from big fish. Therefore, in order to increase the dephosphorization rate, it is necessary to increase the basicity by adding a large amount of flux.
［間通点を解決するための手段］ 上記問題点は、 ３０屯埴％以下のＣｒを含有する溶湯に。[Means for resolving the gap] The above problem is For molten metal containing 30 tons or less of Cr.
・バリウムの酸化物又は炭酸塩３０〜 ７０屯ｆ％。・Barium oxide or carbonate 30~ 70 tons f%.
・アルカリ土類金属のハロゲン化物２０〜６０ｇＡ量％
。・Alkaline earth metal halide 20-60gA amount%
.
・アルカリ金属の炭酸塩１〜２０重量％をｒ成分として
含有するフラックスを添加することにより脱燐を行なう
ことを特徴とするクロムを含む溶湯の脱燐方法によって
解決される。- The problem is solved by a method for dephosphorizing a chromium-containing molten metal, which is characterized by dephosphorizing by adding a flux containing 1 to 20% by weight of an alkali metal carbonate as an r component.
ここで、Ｃｒを含有する溶湯としては、たとえば、Ｆ
ｅ ）５合金、Ｎｔ基合金、Ｃｏ基合金その他のＣｒよ
り酸化されにくい元素を主成分とするＣｒ含有合金の溶
湯である。Ｆｅ基合金には、炭素濃度が数％のＣｒ溶銑
、粗溶鋼も含まれる。Here, as the molten metal containing Cr, for example, F
e) It is a molten metal of a Cr-containing alloy whose main component is an element that is less easily oxidized than Cr, such as 5 alloy, Nt-based alloy, Co-based alloy, etc. Fe-based alloys also include Cr hot metal and crude molten steel with a carbon concentration of several percent.
Ｃｒは３０屯量％以下である。Cr content is 30 tonne percent or less.
３０重量％を越えると、Ｃｒの酸化が著しくなり脱燐は
困難になる。If it exceeds 30% by weight, oxidation of Cr becomes significant and dephosphorization becomes difficult.
バリウムの酸化物（Ｂａｄ）又は炭酸塩（Ｂ ａｃＯ３
）３０〜７０１量％である。Barium oxide (Bad) or carbonate (BacO3
) 30 to 701% by weight.
バリウムの酸化物又は炭酸塩はＰ７０５をスラグ中に固
定する成分であり、その量が多い程Ｐ２Ｏ５を固定しや
すくなるが、その酸があまり多くなるとスラグの融点が
高くなり、また、流動性か悪くなり、スラグ−メタル間
の反応性が■害される。スラグの流動性という点からは
バリウムの醇化物又は炭酸塩は７０％以下にすることが
必要である。Barium oxide or carbonate is a component that fixes P705 in the slag, and the larger the amount, the easier it is to fix P2O5, but if the amount of barium acid is too large, the melting point of the slag will increase, and the fluidity will decrease. The reactivity between slag and metal is impaired. From the viewpoint of fluidity of the slag, it is necessary that the content of barium liquefied or carbonate be 70% or less.
Ｎａ１・ Ｃｏｔ 等のアルカリ・ｂ属の）父酸塩を力
■えることにより、低１１２基度においても脱燐効率を
高くすることが本発明方法の特徴であるが、（Ｂ ａｏ
）／ （Ｓ １０２）＜５ではその効果はない、従って
、（Ｂ ａｏ）／ （Ｓ ｉ Ｏ２）を高く保つために
、ＢａＯは３０％以上にすることが必要である。A feature of the method of the present invention is that the dephosphorization efficiency is increased even at low 112 radicals by strengthening the alkali (B ao group) such as Na1.
)/(S 102)<5, there is no effect. Therefore, in order to keep (B ao)/(S i O2) high, it is necessary to increase BaO to 30% or more.
ＢａＣ０：＋は熱分解（Ｂ ａｃｏｌ ４１３ ａｏ＋
ＣＯ２）Ｌ、てＢａＯとＣＯ２を生成する。BaC0:+ is thermal decomposition (Bacol 413 ao+
CO2) L, which produces BaO and CO2.
ＣＯ２は酸化剤としてＰを酸化する働きがある。そのた
め、ＢａＯの一部又は全部をＢａＣＯ３として添加する
ことも可能である。CO2 acts as an oxidizing agent to oxidize P. Therefore, it is also possible to add part or all of BaO as BaCO3.
アルカリ土類金属のハロゲン化物（ＢａＣｌ２ 。Alkaline earth metal halide (BaCl2.
ＢａＦ７ 等）は２０〜６０％である。BaF7 etc.) is 20 to 60%.
アルカリ土類金属のハロゲン化物は、スラグの融点を低
下させ、流動性を保つため最低２０％を添加することが
必要である。しかし、多すぎると耐火物の損傷が激しく
なるため６０％がＬ限である。Alkaline earth metal halides must be added in an amount of at least 20% in order to lower the melting point of the slag and maintain fluidity. However, if the amount is too large, the refractory will be severely damaged, so 60% is the L limit.
アルカリ金属の炭酩１１１！ （Ｎ ａ２Ｃ０３等）は
１〜２０り６である。Alkali metal charcoal 111! (Na2C03 etc.) is 1-206.
アルカリ金属の炭酸塩は熱分解（Ｎ ａ ２ ＣＯ２−
＋Ｎａｚ Ｏ＋Ｃ（）２ 、に２ ＣＯ３−に２
０＋Ｃ０７）して酸化物としてスラグ中に存在する。こ
れら酸化物は、ＢａＯ／５ｉＯｚが低い場合において脱
燐効率を向上させる働きをする。Carbonates of alkali metals undergo thermal decomposition (N a 2 CO2-
+Naz O+C()2, 2 CO3-2
0+C07) and exists in the slag as an oxide. These oxides serve to improve the dephosphorization efficiency when BaO/5iOz is low.
Ｎａ２ＣＯ３等は１％未満では脱燐効率向上の効果が小
さく、２０％を越えると耐火物侵食及びヒユームの発生
が大きい。When Na2CO3 and the like are less than 1%, the effect of improving the dephosphorization efficiency is small, and when it exceeds 20%, corrosion of refractories and generation of fumes are large.
熱分解のときに生成するＣＯ２は酸化剤としてＰを酸化
する働きをする。CO2 generated during thermal decomposition acts as an oxidizing agent to oxidize P.
Ｐを酸化する成分としては、ＢａＣＯ３及びアルカリ金
属時炭酸塩が熱分解するときのＣＯ２がその］動きをす
る。しかし、酸化力がさらに必要な場合には鉄酸化物、
クロム酸化物等の固体酸化物をフラックスに添加するこ
とができる。The components that oxidize P include BaCO3 and CO2 when alkali metal carbonates are thermally decomposed. However, if more oxidizing power is required, iron oxide,
Solid oxides such as chromium oxide can be added to the flux.
［発明の実施例］
（１）試験方法
小型溶解炉にて鋼材３５０ｇをマグネジするつぼ内で溶
解し、溶鋼表面にフラックスを添加して処理前後の溶＃
４＋＆分の変化を調へた。溶鋼およびフラックスの代表
的成分を表１に示す。[Embodiments of the invention] (1) Test method In a small melting furnace, 350 g of steel is melted in a mag-screw crucible, and flux is added to the surface of the molten steel to determine the melt # before and after treatment.
Adjusted the change of 4+&min. Table 1 shows typical components of molten steel and flux.
実験温度は１５００℃、時間は２０分である。The experimental temperature was 1500°C and the time was 20 minutes.
本実施例ではアルカリ土類金属のハロゲン化物としてＢ
ａＣｌ２．アルカリ金属炭酸塩としてＮａ７ＣＯ１を用
いた。In this example, B is used as the alkaline earth metal halide.
aCl2. Na7CO1 was used as the alkali metal carbonate.
（２）試験結果
表１に、得られた結果の例を示す、スラグ塩基度の影響
を見る為に５ｉ０７ を添加している。このＳｉＯン
は実操業においては不可避的に混入してくる成分である
が、実験上は故意に添加している。(2) Test results Table 1 shows examples of the results obtained. 5i07 was added to see the influence of slag basicity. This SiO
Although it is a component that is unavoidably mixed in actual operation, it is intentionally added in experiments.
表中のＮｏ１〜３は従来技術であり、本発明の実施例と
比較するために行なった。この場合もＳ〜２の添加量が
多い程、すなわち、スラグ塩基１■が小さいほど脱燐効
率は急激に低下する。Nos. 1 to 3 in the table are conventional techniques, and were conducted for comparison with examples of the present invention. In this case as well, the greater the amount of S~2 added, that is, the smaller the slag base 1 is, the more rapidly the dephosphorization efficiency decreases.
Ｎｏ４〜７は本発明の実施例による脱燐方法である。Ｎ
ａ２ ＣＯ＝添加により脱燐効率が非常に良くなること
が分る。Nos. 4 to 7 are dephosphorization methods according to examples of the present invention. N
It can be seen that the addition of a2 CO= greatly improves the dephosphorization efficiency.
図面にスラグ塩基度ｉ脱燐率との関係を示す、なお１図
面に示す実験条件は、
・溶’１４ １０ｃｒ−１，５Ｇ
・処理温度 １５００℃
・フラックス中Ｎａｚ ＣＯ３量 ０〜１５％である。The relationship between slag basicity and dephosphorization rate is shown in the drawing.The experimental conditions shown in the drawing are as follows: - Melt '14 10cr-1.5G - Processing temperature 1500°C - Amount of Naz CO3 in flux 0 to 15% .
図面から明らかなように、同じ塩基度に対し、Ｎａ２Ｃ
Ｏ３を添加した場合には脱燐効率が高くなる。この効果
は塩基度が約５〜３０の範囲で大きい。As is clear from the drawing, for the same basicity, Na2C
When O3 is added, the dephosphorization efficiency increases. This effect is greater when the basicity ranges from about 5 to 30.
（３）実施例と従来例の比較
・脱燐効率
従来例は塩基度の低下と共に急激に脱燐効率が低下する
１本発明の実施例においても脱燐効率は塩基度に依存す
るが、従来例に比べて脱Ｐ効率は高い（図面）。(3) Comparison of Example and Conventional Example - Dephosphorization Efficiency In the conventional example, the dephosphorization efficiency decreases rapidly as the basicity decreases.In the Example of the present invention, the dephosphorization efficiency also depends on the basicity, but in the conventional example, the dephosphorization efficiency decreases rapidly as the basicity decreases. The P removal efficiency is higher than in the example (see the drawing).
・コスト
図面から分るように塩基度が３０以上においては本実施
例の優位性は少ない。しかし、実操業では、脱燐処理前
の脱Ｓｉ、前玉程で発生したスラグの除去を行なっても
ある程度の州のＳｉＯ２の混入は避けられない。そこで
、脱燐率を高くするにはフラックス原単位を高くする必
要がある。これに対し、本発明の実施例では比較的少量
の（実施例では約１０％）のＮａ２ＣＯｚ添加すること
により効率よ〈脱燐を行なうことがでＪる。また、 Ｂ
ａＣＯ３はＮａ２ＣＯ３に比へ安価なことからも本発明
の実施例はコスト的に有利である。- As can be seen from the cost diagram, this example has little advantage when the basicity is 30 or more. However, in actual operation, even if Si is removed before the dephosphorization process and slag generated at the front stage is removed, a certain amount of SiO2 cannot be avoided. Therefore, in order to increase the dephosphorization rate, it is necessary to increase the flux consumption rate. On the other hand, in the examples of the present invention, by adding a relatively small amount (approximately 10% in the examples) of Na2COz, dephosphorization can be carried out efficiently. Also, B
Since aCO3 is cheaper than Na2CO3, the embodiments of the present invention are advantageous in terms of cost.
［発明の効果］
ＰにおいてＮａ２ ＣＯ３を主成分の１つとして添加す
ることにより、低コストで脱燐効Ｍを高くすることが可
能になった。[Effects of the Invention] By adding Na2CO3 as one of the main components to P, it has become possible to increase the dephosphorization effect M at low cost.
図面はスラブ塩基度とＰ分配比の関係に及ぼすＮａｚＣ
Ｏ：＋添加の影響を示すグラフである。The figure shows the effect of NazC on the relationship between slab basicity and P distribution ratio.
It is a graph showing the influence of O:+ addition.
Claims (1)
り脱Ｐを行なうことを特徴とするクロムを含む溶湯の脱
燐方法。[Claims] A molten metal containing 30% by weight or less of Cr: - 30 to 70% by weight of an oxide or carbonate of barium, - 20 to 60% by weight of an alkaline earth metal halide, - an alkali metal. A method for dephosphorizing a molten metal containing chromium, characterized in that dephosphorization is carried out by adding a flux containing 1 to 20% by weight of carbonate as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60253463A JPS62112716A (en) | 1985-11-12 | 1985-11-12 | Dephosphorization method for molten metal containing chromium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60253463A JPS62112716A (en) | 1985-11-12 | 1985-11-12 | Dephosphorization method for molten metal containing chromium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62112716A true JPS62112716A (en) | 1987-05-23 |
Family
ID=17251735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60253463A Pending JPS62112716A (en) | 1985-11-12 | 1985-11-12 | Dephosphorization method for molten metal containing chromium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62112716A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724790A (en) * | 2019-10-31 | 2020-01-24 | 辽宁科技学院 | Steelmaking dephosphorizing agent interface modifier and preparation and use methods of modified dephosphorizing agent |
| US11225695B2 (en) | 2016-12-12 | 2022-01-18 | Posco | Dephosphorizing flux and method for preparing same |
-
1985
- 1985-11-12 JP JP60253463A patent/JPS62112716A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11225695B2 (en) | 2016-12-12 | 2022-01-18 | Posco | Dephosphorizing flux and method for preparing same |
| CN110724790A (en) * | 2019-10-31 | 2020-01-24 | 辽宁科技学院 | Steelmaking dephosphorizing agent interface modifier and preparation and use methods of modified dephosphorizing agent |
| CN110724790B (en) * | 2019-10-31 | 2021-04-13 | 辽宁科技学院 | Steelmaking dephosphorizing agent interface modifier and preparation and use methods of modified dephosphorizing agent |
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